Sulfur production

ABSTRACT

A system includes a first chamber, a second chamber, an ultraviolet light source and a microwave source. The first chamber includes an inlet. The second chamber is adjacent the first chamber and includes an outlet and a waveguide. The ultraviolet light source resides within the waveguide of the second chamber. Related apparatus, systems, techniques and articles are also described.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a divisional of U.S. patent application Ser.No. 15/955,170, entitled “SULFUR PRODUCTION,” filed Apr. 17, 2018, whichclaims priority under 35 U.S.C. § 119(e) to U.S. Patent ProvisionalApplication No. 62/486,489, entitled “SULFUR PRODUCTION,” filed Apr. 18,2017, and U.S. Patent Provisional Application No. 62/522,446, entitled“SULFUR PRODUCTION,” filed Jun. 20, 2017, each of which is incorporatedby reference herein in its entirety.

TECHNICAL FIELD

The subject matter described herein relates to producing sulfur and/orhydrogen from a sulfur compound.

BACKGROUND

Crude oil or petroleum is generally processed and refined in anindustrial refinery and refined petroleum products such as such asasphalt base, fuel oil, diesel, gasoline, kerosene and liquefiedpetroleum gas and the like can be separated based on their differentboiling points. The petroleum products mostly contain varieties ofhydrocarbons having different carbons numbers or structures and alsocontain oxygen compounds such as phenol, ketones, and carboxylic acids,nitrogen compounds such as indole, acridine, hydroxyquinolino, andaniline, sulfur compounds thiol, sulfide, disulfide, tetrahydrothiphene,thiophene, alkylthiophene, benzothiophene, dibenzothiophene, alkyldibenzothiophene, transition metal compounds containing nickel,vanadium, molybdenum and the like, and inorganic salts.

Sulfur compound contained in the petroleum can be released as hydrogensulfide gas (H₂S) that is also included as vast majority in naturalgases and the hydrogen sulfide gas are processed and converted intoelemental sulfur and hydrogen gas, which is known as “desulfurization”.In a certain example in the related art, Claus process produceselemental sulfur from hydrogen sulfide gas released from the refineryprocess by combustion and catalytic chemical reactions.

However, for conventional desulfurization processes, large and complexfacilities are necessary and the chemical reactions duringdesulfurization are corrosive to those facilities. Moreover, efficiencyof the desulfurization processes and operations is not sufficient toyield productivity. Further, other raw materials may be used for thecurrent conventional desulfurization.

SUMMARY

In an aspect, a system includes a first chamber, a second chamber, anultraviolet light source and a microwave source. The first chamberincludes an inlet. The second chamber is adjacent the first chamber andincludes an outlet and a waveguide. The ultraviolet light source resideswithin the waveguide of the second chamber.

One or more of the following features can be included in any feasiblecombination. For example, the microwave source is configured to radiatemicrowave energy into the first chamber and the waveguide of the secondchamber such that the microwave energy contacts the ultraviolet lightsource. The ultraviolet light source includes an internal gas thatgenerates ultraviolet light upon contact with the microwave energy. Thewaveguide can include an end configured such that the microwave energyforms a standing wave within the waveguide. The second chamber canfurther include a first electrode configured to have a negative charge;and a second electrode configured to have a positive charge, the firstelectrode and the second electrode being external to the ultravioletlight source and internal to the waveguide.

The system can include a tube assembly within the waveguide andcontaining the ultraviolet light source, a wall of the tube assembly canbe transparent to ultraviolet light and microwave energy. The firstchamber can be located between the microwave source and the secondchamber such that the microwave energy is generated by the microwavesource and passes through the first chamber to the second chamber.

The system can include a plurality of tube assemblies adjacent the firstchamber, each of the plurality of tube assemblies including a tubeassembly outlet, each tube assembly including a wall that is transparentto ultraviolet light and microwave energy. The system can include aplurality of ultraviolet light sources, each residing within arespective one of the tube assemblies. The microwave source can beconfigured to radiate the microwave energy into the first chamber andinto the plurality of tube assemblies such that the microwave energycontacts the plurality of ultraviolet light sources. The plurality ofultraviolet light sources can include the internal gas that generatesultraviolet light upon contact with the microwave energy.

The system can include a hydrogen sulfide source coupled to the inlet.The system can include a gas-solid separator coupled to the outlet andconfigured to separate sulfur from hydrogen gas.

The ultraviolet light source can radiate the ultraviolet light having awavelength ranges from about 280 nm to 300 nm. The second chamber can beelongate and can extend along a primary axis. The ultraviolet lightsource can be elongate along the primary axis and can reside within thesecond chamber along the primary axis. The second chamber can include afirst electrode configured to have a negative charge and a secondelectrode configured to have a positive charge. The first electrode andthe second electrode can be external to the ultraviolet light source andinternal to the waveguide. The first electrode can be elongate along theprimary axis and can be arranged above the ultraviolet light source. Thesecond electrode can be elongate along the primary axis and can bearranged below the ultraviolet light source.

The second chamber can form a hydrocyclone. The light source can resideon a vortex finder located within the hydrocyclone.

In another aspect, hydrogen sulfide is provided into a first chamberadjacent a second chamber and a microwave source radiating microwaveenergy into the first chamber. The hydrogen sulfide is contacted withmicrowave energy generated by a microwave source. The hydrogen sulfideis provided to the second chamber. The second chamber includes an outletand a waveguide. An ultraviolet light source resides within thewaveguide of the second chamber. The hydrogen sulfide is contacted withultraviolet light within the second chamber. The ultraviolet light isgenerated by the ultraviolet light source. The microwave source isconfigured to radiate the microwave energy into the first chamber andthe waveguide of the second chamber such that the microwave energycontacts the ultraviolet light source. The ultraviolet light sourceincludes an internal gas that generates the ultraviolet light uponcontact with the microwave energy. Contacting of the hydrogen sulfidewith the ultraviolet light results in hydrogen gas and sulfur.

One or more of the following features can be included in any feasiblecombination. For example, the waveguide can include an end configuredsuch that the microwave energy forms a standing wave within thewaveguide. The second chamber can include a first electrode configuredto have a negative charge and a second electrode configured to have apositive charge, the first electrode and the second electrode beingexternal to the ultraviolet light source and internal to the waveguide.The hydrogen sulfide can be provided to a plurality of tube assembliesadjacent the first chamber, each of the plurality of tube assembliesincluding a tube assembly outlet, a plurality of ultraviolet lightsources each residing within a respective one of the plurality of tubeassemblies. The microwave source can be configured to radiate themicrowave energy into the first chamber and into the plurality of tubeassemblies such that the microwave energy contacts the plurality ofultraviolet light sources. The plurality of ultraviolet light sourcescan include the internal gas that generates ultraviolet light uponcontact with the microwave energy.

The sulfur can be separated, using a gas-solid separator, from thehydrogen gas. The ultraviolet light source can radiate the ultravioletlight having a wavelength ranges from about 280 nm to 300 nm. The secondchamber can be elongate and can extend along a primary axis. Theultraviolet light source can be elongate along the primary axis and canreside within the second chamber along the primary axis. The secondchamber can include a first electrode configured to have a negativecharge; and a second electrode configured to have a positive charge, thefirst electrode and the second electrode being external to theultraviolet light source and internal to the waveguide. The firstelectrode can be elongate along the primary axis and can be arrangedabove the ultraviolet light source. The second electrode can be elongatealong the primary axis and can be arranged below the ultraviolet lightsource.

A temperature for decomposing the hydrogen sulfide can be performed at atemperature range of about 0 to 125 degrees Celsius. The hydrogensulfide can be provided into the first chamber at a pressured of 0.1 to10 atm. The ultraviolet light and the microwave energy can be contactedwith the hydrogen sulfide for about 0.01 seconds to 15 minutes. Thehydrogen sulfide can be collected from natural gas or petroleum oil canbe processed to generate the hydrogen sulfide.

In yet another aspect, a system includes a first heat exchanger, asecond heat exchanger, a first separator, a third heat exchanger, afourth heat exchanger, and a second separator. The first heat exchangerincludes a first input, a second input, a first output, and a secondoutput. The second heat exchanger includes a third input, a fourthinput, a third output, and a fourth output. The first output is operablycoupled to the third input. The first separator is operably coupledbetween the third output and the second input. The third heat exchangerincludes a fifth input, a sixth input, a fifth output and a sixthoutput. The fifth input is operably coupled to the first separator. Thefourth heat exchanger includes a seventh input, an eighth input, aseventh output, and an eighth output. The seventh input is operablycoupled to the fifth output. The second separator is operably coupledbetween the seventh output and the sixth input and between the seventhoutput and the fourth input.

One or more of the following features can be included in any feasiblecombination. For example, the first heat exchanger can be configured totransfer heat between a stream provided to the first input and a streamprovide to the second input. The stream provided to the first input canexit the first output and the stream provided to the second input canexit the second output. The second heat exchanger can be configured totransfer heat between a stream provided to the third input and a streamprovide to the fourth input. The stream provided to the third input canexit the third output and the stream provided to the fourth input canexit the fourth output. The third heat exchanger can be configured totransfer heat between a stream provided to the fifth input and a streamprovide to the sixth input. The stream provided to the fifth input canexit the fifth output and the stream provided to the sixth input canexit the sixth output. The fourth heat exchanger can be configured totransfer heat between a stream provided to the seventh input and astream provide to the eighth input. The stream provided to the seventhinput can exit the seventh output and the stream provided to the eighthinput can exit the eighth output.

The first separator can be configured to separate liquid and gas and thesecond separator can be configured to separate liquid and gas.

The system can include a cooling unit operably coupled to the eighthinput and the eighth output. The system can include a gas source coupledto the first input and providing a gas including hydrogen sulfide,carbon dioxide, and methane to the first input. The system can include amethane holding unit operatively coupled to the sixth output. The systemcan include a carbon dioxide holding unit operatively coupled to thefourth output. The system can include a hydrogen sulfide holding unitoperatively coupled to the second output.

The second heat exchanger and the first separator can comprise a firstcondenser. The fourth heat exchanger and the second separator cancomprise a second condenser. The system can include a photo-reactor asdescribed above in which the second output is operatively coupled to theinlet of the first chamber.

The details of one or more variations of the subject matter describedherein are set forth in the accompanying drawings and the descriptionbelow. Other features and advantages of the subject matter describedherein will be apparent from the description and drawings, and from theclaims.

DESCRIPTION OF DRAWINGS

FIG. 1 shows a graph of rate constant for dissociating hydrogen sulfide(H₂S) into hydrogen gas and sulfur.

FIG. 2 shows exemplary processes of producing sulfur from natural gasaccording to an exemplary embodiment of the present subject matter.

FIG. 3 shows exemplary processes of producing sulfur from diesel ordiesel vapor according to an exemplary embodiment of the present subjectmatter.

FIG. 4A illustrates an exemplary reactor according to an exemplaryembodiment of the present subject matter.

FIG. 4B illustrates an exemplary reactor according to an exemplaryembodiment of the present subject matter.

FIG. 5 is a block diagram illustrating an example.

FIGS. 6 and 7 illustrate photographs of the example.

FIG. 8 is a longitudinal cross section of an example photo-reactor fordecomposing hydrogen sulfide into hydrogen gas and sulfur.

FIG. 9 is a cross-sectional view of a tube assembly.

FIG. 10 illustrates the photo-reactor of FIG. 8 with a standing wave.

FIG. 11 is a cross-sectional view of another example photo-reactorhaving multiple tube assemblies.

FIGS. 12-17 are views of an example photo-reactor according to someimplementations of the current subject matter.

FIG. 18 illustrates an example system for decomposing hydrogen sulfide.

FIGS. 19-25 illustrate various views of the example system of FIG. 18.

FIGS. 26-29 illustrate views of an example microwave source.

FIG. 30 is a system block diagram illustrating the example processingflow of desulfurization.

FIG. 31 is a system block diagram illustrating a system block diagram ofexample process for a biogas distillery for processing raw gas.

FIG. 32 is an example system for implementing the example processillustrated in FIG. 31.

FIGS. 33-35 are views illustrating an example gas-solid separator.

FIGS. 36-41 illustrate various views of an example array ofphoto-reactors.

FIGS. 42-48 illustrate various views of exemplary reactors according toexemplary embodiments of the present subject matter.

Like reference symbols in the various drawings indicate like elements.

DETAILED DESCRIPTION

The term “reactor” as used herein refers to a chamber or vessel where achemical reaction may occur. The reactor may be provided to maintain acertain volume for the reaction, and further provided with a function tocontrol a temperature and/or a pressure of the reactions.

The term “sulfur” and “sulfur product” as used herein, refers tocompounds comprising elemental sulfur. In certain embodiments, theelemental sulfur may exist in solid state, polyatomic molecules such asS₆, S₇, S₈, S₉ or Sit, S₁₈ in normal conditions.

The term “dissociation” refers to bond breaking between at least twoatoms.

The term “bond dissociation energy” refers to an amount of energyrequired to breaking a bond between at least two atoms.

The term “radiating” refers to emitting an energy in form of light orheat to an object.

The terminology used herein is for the purpose of describing particularembodiments only and is not intended to limit the subject matter. Asused herein, the singular forms “a”, “an” and “the” are intended toinclude the plural forms as well, unless the context clearly indicatesotherwise. It will be further understood that the terms “comprises”and/or “comprising,” or “includes” and/or “including,” when used in thisspecification, specify the presence of stated features, regions,integers, steps, operations, elements and/or components, but do notpreclude the presence or addition of one or more other features,regions, integers, steps, operations, elements, components and/or groupsthereof.

Unless specifically stated or obvious from context, as used herein, theterm “about” is understood as within a range of normal tolerance in theart, for example within 2 standard deviations of the mean. “About” canbe understood as within 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%,0.1%, 0.05%, or 0.01% of the stated value. Unless otherwise clear fromthe context, all numerical values provided herein are modified by theterm “about.”

The present subject matter can include producing sulfur or sulfurproduct that includes substantially homogenous elemental sulfur. Theelemental sulfur may be obtained from desulfurization process, forexample, by removing sulfur containing compounds from natural gas, coal,crude oil or petroleum, and converting the removed sulfur containingcompounds into elemental sulfur. The current subject matter is notlimited to processing fuels but can extend to other applications, suchas desulfurizing within a molasses processing facility, which cancontain large amounts of hydrogen sulfide, and biogas from a wastetreatment facility.

In some implementations, desulfurization may be performed by radiatinghydrogen sulfide with microwaves and UV light to decompose hydrogensulfide into hydrogen and elemental sulfur. The microwaves can serve tothermally excite the hydrogen sulfide, thereby beneficially causing bondvibration and increasing bond length, and the UV light can cause bonddisassociation. As a result, the present systems and methods do notinvolve ionization, but rather involve cleaving the hydrogen sulfidebonds. The thermal excitation of the hydrogen sulfide advantageouslyincreases the ability of the hydrogen sulfide to absorb the UV light,resulting in greater bond dissociation and consequently, elementalsulfur production. Furthermore, the thermal excitation of the hydrogensulfide provides the ability to effect bond disassociation using higherUV wavelengths, which have greater bond penetration power, andtherefore, result in a more effective cleaving of the hydrogen bondsthat would not otherwise occur with lower UV wavelengths.

Furthermore, in some implementations, the microwaves can form a standingwave, which, due to the polarity of hydrogen sulfide, can adjustmolecular position of the hydrogen sulfide thereby increasing effectiveUV absorption area, thereby increasing elemental sulfur production,compared to when a standing wave is not used. An electrodeless UV lampcan be used as the UV light source and the UV lamp can be driven by themicrowave source that is also radiating the hydrogen sulfide.

Hydrogen sulfide (H₂S) gas can be abundantly produced during oilrefinery processes or can be collected as components of natural gases.Accordingly, hydrogen sulfide may be provided useful resources forsulfur production. Hydrogen sulfide may be decomposed into hydrogen gasand elemental sulfur using the present system and methods resulting inhigher yields, as compared to conventional systems and methods. This isbecause, as compared to conventional systems and methods, the presentsystems and methods can dissociate S—H bonds at a faster rate, therebydecreasing retention time, and dissociate S—H bonds using lower amountsof energy. As a result, the formation of other species during bonddisassociation can be reduced or minimized.

Hydrogen sulfide comprises two S—H bonds which can be dissociated uponenergy input. The hydrogen sulfide bond in H₂S may be broken ordissociated sequentially. For example, a first bond may be broken whensufficient energy greater than the first bond dissociation energy, e.g.,381 KJ/mol at 298K, is applied, and a second may be broken when theenergy greater than the second bond dissociation energy, e.g. 344 KJ/molat 298K, is applied.H₂S(g)→S(s)+H₂(g)  (1)H₂S→H+SH 381 KJ/mol  (2) first S—H bond breaking (at a temperature of298K)H—S→H+S 344 KJ/mol  (3) second S—H bond breaking (at a temperature of298K)

In FIG. 1, theoretical rate constant for the reaction (1) is shownwithin various temperature ranges. For instance, the rate constant maybe determined by activation energy for the decomposition reaction of thehydrogen sulfide at certain temperature conditions.

However, without wishing to be bound to the theory, the first and seconddissociation of the hydrogen sulfide bonds may be initiated andperformed by supplying sufficient energy to the hydrogen sulfidereactant molecules. The energy for dissociating S—H bonds of hydrogensulfide may be supplied by radiating light. For example, the lightradiation may be within ultraviolet light range. The following Table 1list energy of UV light at various wavelengths.

Type of UV Wavelength λ energy light (nm) (kJ) UV-C 100 1196.66 1101087.87 120 997.21 130 920.50 140 854.75 150 797.77 160 747.91 170703.92 180 664.81 190 629.82 200 598.33 210 569.84 220 543.93 230 520.29240 498.61 250 478.66 260 460.25 270 443.21 280 427.38 UV-B 290 412.64300 398.89 310 386.02 320 373.95 UV-A 330 362.62 340 351.96 350 341.90360 332.40 370 323.42 380 314.91 390 306.83 400 299.16

UV light having sufficient energy to break the first and the second S—Hbond of hydrogen sulfide light may be irradiated for suitably time,until desired amount or yield of producing sulfur is obtained. Forexample, UV radiation may be performed for about 0.01 seconds to 15 min,about 1 second to 30 seconds, or about 0.01 seconds to 15 seconds. It isalso contemplated that the UV radiation may be performed for an amountof time that does not fall outside any of these recited ranges.

Further, each dissociation of S—H bonds may be initiated and performedin various temperature ranges. Preferably, the temperature may rangefrom about 27° C. to 35° C., from about 20° C. to 40° C., or from about0° C. to 125° C. For example, the bond dissociation energy of hydrogensulfide or the activation energy for initiating the reaction may vary indifferent temperature ranges and the energy required for reactions (1)to (3) may be suitably determined based on reaction temperature. It isalso contemplated that the temperature does not fall outside any ofthese recited ranges.

Hydrogen sulfide for producing the sulfur may be substantiallyhomogeneous homogeneity greater than about 80 vol %, 85 vol %, 90 vol %,95 vol %, or 99 vol %. In some embodiments, the hydrogen sulfide may becompressed to have a pressure of about 1 bar to 200 bar. In certainembodiments, the hydrogen sulfide is compressed to have a pressure ofabout 0.1 atm to 10 atm, of about 0.1 atm to 1 atm, or of about 0.1 atmto 0.5 atm. It is also contemplated that the pressure does not falloutside any of these recited ranges.

In some embodiments, the hydrogen sulfide may be heated or supplied inthe form of hot gas (generated via microwave) depending at least in parton the feed temperature of the hydrogen sulfide into the system. Incertain embodiments, the hydrogen sulfide is heated or suppled as a hotgas at a temperature of about 25° C. to 200° C., of about 80° C. to 120°C., of about 100° C. It is also contemplated that the temperature doesnot fall outside any of these recited ranges. It is further contemplatedthat the temperature can be between any of these recited values.

In other embodiments, the hydrogen may be heated or supplied in the formof a vapor.

The decomposed hydrogen sulfide produces hydrogen gas and elementalsulfur. The sulfur product may be obtained in a solid form havingmolecular formula such as S₆, S₇, S₈, S₉ or Sit, S₁₈ after the reactionis completed. The sulfur product may be substantially homogeneous andinclude homogeneity greater than about 80 atom %, 85 atom %, 90 atom %,95 atom %, or 99 atom %. Preferably, the sulfur product may be in formsof particles having an average diameter less than about 5 mm, less thanabout 1 mm, less than about 900 μm, less than about 800 μm, less thanabout 700 μm, less than about 600 μm, less than about 500 μm or of about100 μm to 500 μm. In addition, hydrogen gas may be collected as beingseparated from the sulfur product and may have homogeneity greater thanabout 80 vol %, 85 vol %, 90 vol %, 95 vol %, or 99 vol %. In someimplementations, the sulfur can be amorphous.

The present subject matter can include a method of producing sulfur orelemental sulfur by desulfurization process. The method can includeproviding hydrogen sulfide into a reactor and decomposing the hydrogensulfide.

The hydrogen sulfide may be supplied continuously. In some embodiments,the hydrogen sulfide gas may be supplied or provided to maintain thepartial pressure thereof in the reactor of about 0.1 atm to 10 atm, ofabout 0.1 atm to 1 atm, or of about 0.1 atm to 0.5 atm. It is alsocontemplated that the pressure does not fall outside any of theserecited ranges.

Alternatively, the initial pressure of the hydrogen sulfide in thereactor may be of about 0.1 atm to 10 atm, of about 0.1 atm to 1 atm, ofabout 0.1 atm to 0.5 atm. It is also contemplated that the initialpressure does not fall outside any of these recited ranges. It isfurther contemplated that the initial pressure can be between any ofthese recited values.

The reactor may have a temperature range of about 27° C. to 35° C., from20° C. to 40° C., or from about 0° C. to about 125° C., oralternatively, the decomposition of the hydrogen sulfide may beperformed at a temperature range of 27° C. to 35° C., from 20° C. to 40°C., or from about 0° C. to about 125° C. For example, the reactor may beheated using flame, electric furnace, air stream or the like. In oneembodiment, the decomposition of the hydrogen sulfide may be performedat about ambient temperature. It is also contemplated that thetemperature does not fall outside any of these recited ranges. In otherembodiments, the temperature may be between any of these recited values.

Energy can be supplied to decompose the hydrogen sulfide in the reactor.The energy source for decomposition or dissociating the hydrogen sulfidemay be UV light. The UV light may have a wavelength ranging from about100 nm to about 300 nm, from about 200 nm to about 300 nm, from about280 nm to about 300 nm, or from about 290 nm to about 300 nm. UV lightmay be radiated for about 0.01 seconds to 15 min, about 1 second to 30seconds, or about 0.01 seconds to 15 seconds. It is also contemplatedthat the UV light may be radiated for a period of time that does notfall outside any of these recited time ranges. It is furthercontemplated that the UV light may be radiated for a period of timebetween any of these recited values.

In an exemplary embodiment of the present subject matter, a method ofproducing sulfur from natural gas is provided. As shown in FIG. 2,natural gases (e.g. methane mixtures) containing large quantities ofhydrogen sulfide (H₂S) or other sulfur compounds may be desulfurized.The desulfurization method may not be particularly limited and anymethods generally used in the oil refinery can be used withoutlimitation.

The natural gas may be processed, e.g. drying, to remove water or watervapor (H₂O), and further processed to separate hydrogen sulfide andcarbon dioxide (CO₂). While not necessary, this separation of thehydrogen sulfide from water vapor and carbon dioxide is found to bebeneficial in that it minimizes the presence of oxygen during thepresent desulfurization process. Without wishing to be bound to a singletheory, it is believed that the presence of oxygen during thedesulfurization process negatively impacts the efficiency of the presentdesulfurization process. The separated hydrogen sulfide may betransferred to a reaction chamber where decomposition reaction mayoccur. The hydrogen sulfide may be present in hot vapor or gas phase atthe controlled temperature and partial or internal pressure thereof. Thedecomposition may be performed by radiating UV light until desiredproduct yield is obtained.

In an exemplary embodiment of the present subject matter, a method ofproducing sulfur from diesel (petroleum oil) is provided. As shown inFIG. 3, diesel oil containing sulfur compounds may be desulfurized asdescribed above. For example, diesel may be vaporized and by addinghydrogen gas, hydrogen sulfide may be produced from the sulfur compoundsin the diesel vapor, the hydrogen sulfide gas may be separatedsubsequently. The separated hydrogen sulfide may be transferred to areactor for producing sulfur product. The hydrogen sulfide may bepresent in hot vapor or gas phase at the controlled temperature andpartial or internal pressure thereof. The decomposition may be performedby radiating UV light until desired product yield is obtained.

UV light radiation for decomposing hydrogen sulfide gas may also becontinuously controlled based on initial reaction condition, e.g.temperature and pressure of initial reactant gas (hydrogen sulfide), orby monitoring product yield. UV light radiating device may becontinuously controlled by adjusting parameters such as time, intensityor wavelength.

The method of producing sulfur may include separating and collecting thesulfur product from the hydrogen gas after bond disassociation. Thehydrogen gas may be ventilated, e.g., via outlet of the reactor, or thehydrogen gas may be filtered using a gas permeable membrane. In someembodiments, the hydrogen gas may be separately collected and recycled.

The method of producing sulfur may further comprise cooling the sulfurproduct. The cooled sulfur product may be stabilized and particulated.For example, thus produced sulfur may be formed in particles asdescribed above, e.g., microparticles, such that the processed sulfurproduct can be used as raw materials for various chemical reactions andprocesses.

FIG. 8 is a longitudinal cross section of an example photo-reactor 800for decomposing hydrogen sulfide into hydrogen gas and sulfur. Thephoto-reactor 800 can be coupled to a hydrogen sulfide source (e.g., ina hydrocarbon processing facility) and/or coupled to a gas-solidseparator to separate sulfur from hydrogen gas. The photo-reactor 800can include a microwave source 805, a first chamber 810, a secondchamber 815, and a third chamber 835. The photo-reactor 800 can beformed in a generally cylindrical shape (e.g., a tube).

The first chamber 810 can include an inlet 812 for receiving an inputstream including hydrogen sulfide. The first chamber 810 can be adjacentthe second chamber 815 and the input stream can include hydrogen sulfideand can flow from the first chamber 810 into the second chamber 815through an opening 814. The first chamber 810 can be formed of asuitable material for petroleum processing such as stainless steel.

The second chamber 815 can be elongate and cylindrical along a primaryaxis. The second chamber 815 can include a waveguide 820, which, in theillustrated example, is formed by a wall of the second chamber 815. Thesecond chamber 815 is thus formed of a suitably conductive material suchas stainless steel. In some implementations, the waveguide 820 may beformed by another structure. The waveguide 820 includes a firstwaveguide end 822 at an end of the second chamber 815 that isnon-adjacent the first chamber 810, and a second waveguide end 824 thatis adjacent the first chamber 810. As illustrated in FIG. 8, the firstwaveguide end 822 is integral with an end of the second chamber 815. Thesecond chamber 815 can include an outlet 826 that is non-adjacent thefirst chamber 810.

A tube assembly 830 can reside within the second chamber 815 and canextend along a primary axis of the second chamber 815. An ultravioletlight source 825 can also reside within the tube assembly 830. Inaddition the ultraviolet light source 825, a negative electrode 827 anda positive electron 829 can reside within the tube assembly 830. Thenegative electrode 827 and the positive electrode 829 can be external tothe ultraviolet light source 825 and internal to the waveguide 820. Thenegative electrode 827 and positive electrode 829 can be plate shaped.The negative electrode 827 can be located or arranged above theultraviolet light source 825 and the positive electrode 829 can belocated or arranged below the ultraviolet light source 825. FIG. 9 is across-sectional view of the tube assembly 830. The cross-sectional viewillustrated in FIG. 9 is perpendicular to the cross-sectional view ofFIG. 8.

In other embodiments, in addition to the ultraviolet light source 825, aproton exchange membrane can reside within the tube assembly 830.

In some implementations, a wall 832 of the tube assembly 830 istransparent to both ultraviolet light and microwave energy. The wall 832may be formed of a suitably transparent material such as quartz. In someimplementations, the wall 832 extends from an inner surface to thewaveguide 820. The quartz or other suitably appropriate material (e.g.,glass) can provide structural support as well as be transparent toultraviolet light and microwave energy.

The ultraviolet light source 825 can include an electrodeless lamp,which can include a gas discharge lamp in which the power required togenerate light is transferred from outside the lamp to gas inside via anelectric or magnetic field. This is in contrast with a gas dischargelamp that uses internal electrodes connected to a power supply byconductors that pass through the lamp. There can be a number ofadvantages to an electrodeless lamp, including extending lamp lifebecause electrodes can fail, and power savings because internal gasesthat are higher efficiency can be used that would react if in contactwith an electrode.

Further, one of ordinary skill will appreciate that the use of anelectrodeless lamp, as opposed to plasma, in the systems and methodpresented herein can have advantages. For example, compared to plasma,one advantage to using the electrodeless lamp is the cost-savingsbecause plasma is highly dependent on, and therefore consumes asubstantial amount of, electricity. Another advantage can include theextended lifetime of the electrodeless lamp relative to plasma.Unfortunately, due to high temperatures that can be generated by theplasma arc, decreased arc mobility, etc., the electrodes can prematurelyfail or erode during use, thereby decreasing electrode lifetime.Moreover, using plasma as a radiation source can have its own drawbacks,such as ignition, sustainability, and confinement.

The ultraviolet light source 825 can generate light within a range ofwavelengths, for example, between 100 um and 300 um, between 280 um and300 um, and the like. The gas contained in the lamp can include: argon,mercury, and iodine. In some implementations, the lamp can include argonat 25 KPa and 20 mg of mercury. Other gases, amounts, and pressures arepossible.

The second chamber 815, ultraviolet light source 825, negative electrode827, and positive electrode 829 can be elongate and extend along theprimary axis of the second chamber 815.

The third chamber 835 can be adjacent the second chamber 815 and caninclude two outlets (first outlet 837 and second outlet 839). The thirdchamber 835 can serve as an initial separation space for extractinghydrogen gas through the first outlet 837 and sulfur and any othermaterials present through the second outlet 839. In someimplementations, the third chamber 835 can include a gas-solid separatorsuch as a cyclone and need not be integral with the second chamber 815.

The microwave source 805 can be adjacent the first chamber 810 and caninclude an emitter 807 for radiating microwave energy. The microwavesource 805 can emit electromagnetic energy at frequencies between 200MHz and 300 GHz (corresponding wavelengths between 100 cm and 0.1 cm).In one implementation, the microwave source 805 emits electromagneticenergy at frequencies between about 900 MHz and 2.45 GHz. In someimplementations, the microwave source 805 emits electromagnetic energyat a frequency of about 2.45 GHz. It is also contemplated that thepresent microwave source can emit microwaves at a frequency between anyof these recited values.

The microwave source 805 can be arranged to radiate microwave energyinto the first chamber 810 and the waveguide 820 of the second chamber815 and to contact the ultraviolet light source 825. When the microwaveenergy contacts the ultraviolet light source 825, the ultraviolet lightsource 825 can generate ultra violet light. In some implementations, themicrowave source 805 can be arranged to radiate microwave energy so thatthe microwave energy passes through the first chamber 810 to reach thesecond chamber 815. The microwave energy produced by the microwavesource 805 can thermally excite hydrogen sulfide residing within thefirst chamber 810 and simultaneously drive/excite the ultraviolet lightsource 825. Such an arrangement can be efficient in that little radiatedenergy is lost because it can serve to both thermally excite thehydrogen sulfide and generate the ultraviolet light, both of whichcontribute to bond disassociation (e.g., creating hydrogen gas andelemental sulfur from hydrogen sulfide). Moreover, this arrangement canenable tuning of the microwave source such that only the amount ofenergy needed for bond disassociated is input to the system with littleenergy wasted to unnecessary thermal heating.

First waveguide end 822 and second waveguide end 824 can be formed suchthat the second chamber 815 and/or waveguide 820 serves as a resonatorbecause microwave energy radiated into the second chamber 815 isreflected. This arrangement can result in the formation of a standingwave within the second chamber as a result of interference between wavesreflected back and forth within the second chamber 815 and/or waveguide820. A standing wave (also referred to as a stationary wave) can includea wave in which each point on the axis of the wave has an associatedconstant amplitude. For example, FIG. 10 illustrates the photo-reactor800 of FIG. 8 with a standing wave 1005 illustrated. Locations at whichthe amplitude is minimum are called nodes and locations where theamplitude is maximum are called antinodes. The photo-reactor 800 can bedesigned/controlled such that positive amplitude values of the standingwave are positioned on the positive electrode 829 and negative amplitudevalues of the standing wave are positioned on the negative electrode827.

In operation, a flow of hydrogen sulfide gas is introduced into inlet812 under a pressure and a temperature. The hydrogen sulfide gas iscontacted with microwave energy in the form of microwaves radiated bythe microwave source 805. When contacted with microwave energy, thehydrogen sulfide is thermally excited. The thermally excited hydrogensulfide flows into the second chamber 815 including into the interior ofthe tube assembly 830. The thermally excited hydrogen sulfide iscontacted with the standing wave. Because hydrogen sulfide is polar inthat the molecule has an uneven distribution of electrons, the moleculehas a positively charged side and a negatively charged side. Thehydrogen sulfide in the presence of the standing wave will align (e.g.,orient) itself with the standing wave. This will increase the molecule'seffective cross-sectional area for ultraviolet light absorption. As aresult, hydrogen sulfide exposed to a standing wave and ultravioletlight will absorb more energy from the ultraviolet light than hydrogensulfide that is not in the presence of a standing wave.

The thermally excited hydrogen sulfide exposed to ultraviolet light canresult in bond disassociations and the creation of hydrogen ions (H⁺)and sulfur ions (S²⁻). The hydrogen can be attracted to the negativeelectrode 827 and the sulfur can be attracted to the positive electrode829. This can cause the hydrogen and sulfur to physically separate,which reduces the amount and likelihood that these radicals will reactto form hydrogen sulfide. This can act as a form of quenching (e.g.,stopping or reducing the reverse reaction). The negative electrode 827can be arranged above the positive electrode 829 because the hydrogen islighter than the sulfur (thus the sulfur will be pulled downwards bygravity). Alternatively, the positive and negative electrodes 827, 829can be replaced with a proton exchange membrane which can act as a formof quenching.

The resident time of the hydrogen sulfide within the second chamber 815can be controlled by controlling the length of the second chamber 815and the flow rate of the hydrogen sulfide into the photo-reactor 800. Inaddition, the energy imparted by the microwave source 805 and theultraviolet light source 825 to the hydrogen sulfide can affect therequired resident time.

The hydrogen and sulfur can exit the second chamber 815 through thesecond chamber outlet 823 and hydrogen, being lighter, can exit throughthe first outlet 837 while sulfur, being heavier, can exit through thesecond outlet 839. In some implementations, a gas-solid separator suchas a cyclone can be used.

While the above example operation has been described with pure hydrogensulfide provided as input to the photo-reactor 800, contaminants canalso be included. Common contaminants can include carbon dioxide,methane, and other hydrocarbons. These contaminants can exit thephoto-reactor 800 through the second outlet 839 along with the sulfur.By reducing the amount of contaminants in the hydrogen sulfide, energyefficiency in the system is improved because more energy is consumedwhen the contaminants are exposed to the microwave energy andultraviolet light.

In addition, the frequencies/wavelengths of ultraviolet light generatedby the ultraviolet light source 825 can be varied by controlling and/ormodifying the microwave source 805. By changing the frequency/wavelengthof the microwave energy, the frequency of the light generated by theultraviolet light source 825 can change. Changing thefrequency/wavelength of the ultraviolet light can enable an operator totune the photo-reactor 800 based on the expected contaminants in theinput stream to improve efficiency. The ultraviolet lightfrequencies/wavelengths can be tuned to frequencies/wavelengths wherethe hydrogen sulfide has a higher absorption coefficient and thecontaminants have a lower absorption coefficient. Thus, someimplementations of the photo-reactor 800 need not be redesigned for eachapplication.

Some implementations can include multiple tube assemblies 830 arrangedin parallel. For example, FIG. 11 is a cross-sectional view of anotherexample second chamber 815 having multiple tube assemblies 830. Thecross-sectional view illustrated in FIG. 11 is perpendicular to thecross-sectional view of FIG. 8. The tube assemblies 830 are arrangedwithin the second chamber 815 and each can have its own ultravioletlight source 825, negative electrode 827 and positive electrode 829. Aregion 1105 between the tube assemblies can be formed of a material thatis transparent to both ultraviolet light and microwave energy, such asquartz. The arrangement of FIG. 11 allows for light emitted from oneultraviolet light source 825 to not only illuminate hydrogen sulfidewithin its tube assembly 830 but to also illuminate hydrogen sulfidewithin the other tube assemblies 830. The multiple ultraviolet lightsources 825 can be excited/driven by a common microwave source 805 andreside within a common waveguide. In some implementations, each tubeassembly 830 includes a respective waveguide 820.

FIGS. 12-17 are views of an example photo-reactor 800 according to someimplementations of the current subject matter.

FIG. 18 illustrates an example system 1800 for decomposing hydrogensulfide. The system 1800 includes a photo-reactor 800, hydrogen sulfidesource 1805, and gas-solid separator 1810. FIGS. 19-25 illustratevarious views of the example system 1800.

FIGS. 26-29 illustrate views of an example microwave source 805. In theillustrated example, the microwave source 805 is a magnetron.

FIG. 30 is a system block diagram illustrating the example processingflow 3000 of desulfurization. At 3010, hydrogen sulfide is provided. At320, the hydrogen sulfide is present in a process tube (e.g., firstchamber 810). At 3030, the hydrogen sulfide is split using photolysis(e.g., in a second chamber 815). At 3040, a separator (e.g., a cyclone)3040 separates the split hydrogen sulfide into hydrogen gas 3050 andsulfur 3060.

FIG. 31 is a system block diagram illustrating an example system 3100for a waste distillery for processing raw gas. Raw gas can includehydrogen sulfide, carbon dioxide, and methane. The raw gas may beproduced from, for example, animal waste. The system 3100 removeshydrogen sulfide, carbon dioxide, and methane from the raw gas andfurther can decompose the hydrogen sulfide into hydrogen gas and sulfur.System 3100 can include one or more energy recycling circuits that feedsa cold stream from further down in the process back to cool an inputstream for further processing. This approach recycles energy and reducesthe load on cooling units.

System 3100 includes a raw gas receiving unit 3105, a raw gas pre-cooler3110, a hydrogen sulfide condenser 3115, a carbon dioxide sub-cooler3120, a carbon dioxide condenser 3125, and a post cooler tank 3130.

Raw gas receiving unit 3105 receives raw gas including hydrogen sulfide,carbon dioxide, and hydrocarbons such as methane. The raw gas isprecooled at raw gas pre-cooler 3110, which reduces the temperature ofthe raw gas. The raw gas pre-cooler 3110 can include a heat exchangerthat exchanges heat with a hydrogen sulfide output stream 3112 (e.g.,exchanges heat between input streams raising the temperature of thehydrogen sulfide output stream 3112 while lowering the temperature ofthe raw gas stream). The cooled raw gas can be condensed at hydrogensulfide condenser 3115. The hydrogen sulfide condenser 3115 can separatehydrogen sulfide from the raw gas thereby creating hydrogen sulfideoutput stream 3112 and desulfurized raw gas stream 3117. Hydrogensulfide output stream 3112 can be a liquid and can be recycled throughraw gas pre-cooler 3110 as described above.

The desulfurized raw gas 3117 includes carbon dioxide and methane ingaseous phase, which is subsequently cooled at carbon dioxide sub-cooler3120. Carbon dioxide sub-cooler 3120 can include a heat exchanger thattakes the desulfurized raw gas 3117 as a hot input stream and furthertakes a cooled methane stream 3132 as a cold input stream. Carbondioxide sub-cooler 3120 raises the temperature of the cooled methanestream 3132 while lowering the temperature of the desulfurized raw gas3117. Carbon dioxide condenser 3125 can condense carbon dioxide from thedesulfurized raw gas 3117. Carbon dioxide condenser 3125 can separatethe carbon dioxide and methane thereby producing a carbon dioxide outputstream 3122 and a methane stream 3127. Carbon dioxide output stream 3122can be recycled through hydrogen sulfide condenser 3115 as the coldinput stream to the heat exchanger. Similarly, methane stream 3127 canbe stored in a post cooler tank 3130, the output of which can be methanestream 3132, which can be used as the cold input stream to the heatexchanger of the carbon dioxide sub-cooler 3120. The cooled methanestream 3137 can be stored in a storage tank 3140.

The carbon dioxide condenser 3125 can be driven by a carbon dioxidethermal electric cooling element 3145, which includes a circuit forcooling a liquid, which is used by carbon dioxide condenser 3125 tocondense/separate the carbon dioxide and methane. The carbon dioxidecondenser 3125 can include a heat exchanger for exchanging heat betweenthe cooled stream from the thermal electric cooling element 3145 and therelatively warmer carbon dioxide and methane gas received from thecarbon dioxide sub-cooler 3120. Although the example illustrates athermal electric cooling element, other cooling elements are possible.

Because the system 3100 recycles output streams 3112, 3122, and 3132 inorder to perform cooling at steps that occur earlier in the process, therequired cooling load on the carbon dioxide thermal electric coolingelement is reduced.

Once the carbon dioxide output stream 3122, which can be a liquid whenentering hydrogen sulfide condenser 3115, is warmed, it can be providedas an output gas 3147. Similarly, once hydrogen sulfide output stream3112, which can be a liquid when entering raw gas pre-cooler 3110, iswarmed, it can be provided as an output gas 3150.

In some implementations, the output hydrogen sulfide gas 3150 can bedecomposed into sulfur 3155 and hydrogen 3160 using a photo-reactor 800as described above with respect to FIG. 8 and a gas-solid separator1810.

At 3120, the raw gas is cooled to separate the hydrogen sulfide fromhydrocarbons (such as methane) and other contaminants (such as carbondioxide). At 3130, the removed hydrogen sulfide can be processed toproduce sulfur and hydrogen gas, for example, using the processdescribed in FIG. 30. At 3140, the hydrogen sulfide free hydrocarbon andother contaminants may be processed.

FIG. 32 is a system block diagram of a variation of the example system3100 illustrated in FIG. 31.

FIGS. 33-35 are views illustrating an example gas-solid separator 1810in the form of a cyclone.

In some implementations, an array of photo-reactors can be used inparallel to scale any process. For example, FIGS. 36-41 illustratevarious views of an example array of photo-reactors. Each photo-reactorincludes a chamber through which the hydrogen sulfide can pass. Withinthe chamber is at least one ultraviolet light source for irradiating thehydrogen sulfide and decomposing the hydrogen sulfide into hydrogen andsulfide. In FIG. 36, the array of reactors includes 9 reactors (3×3array) that can divide an input stream into 9 separate streams andprocess each stream independently and in parallel. The 9 output streamscan be recombined for further processing or can be maintained asseparate streams. Other implementations are possible, for example, FIG.41 illustrates a 5 ultraviolet light chamber. Another exemplary array ofphoto-reactors is shown in FIG. 48 in which the array of photo-reactors2000 includes 4 photo-reactors 2000 a, 2000 b, 2000 c, and 2000 d.

Another example system or apparatus according to the current subjectmatter can include an electronic module, lamp module, microwave module,reactor module, sensor module, extraction module, mounting structure,pipes/fittings, control module, blower module, separator/recoverymodule, and a safety module. The electronic module can include amicrocontroller and a power controller. The lamp module can include anelectrode less lamp and a lamp mounting. The microwave module caninclude a magnetron, power unit, and a wave guide. The reactor modulecan include a continuously stirred reactor (CSTR), mounting, sensor'sports (thermal, pressure, flow, UV, H₂ sensor, H₂S sensor, multi-gassensors, and the like), and wiring harnesses/conduits. The sensor modulecan include temperature, pressure, UV, flow, valve/actuator position,and gas sensors (H₂, CH₄, CO₂ and the like). The extraction module caninclude a cyclone, cooling coil, thermoelectric coolers, electrodes(e.g., plates) for recovering radicals, and gate/valve actuator. Themounting structure can include a tube, cyclone, microwave module, sensormodule, electronic module, frame and (angles, channels, beams, and thelike). Piping and fittings can include pipes, elbows, reducers, tees,plugs, and valves. Command and control module can include a computer anddata acquisition board. Safety module can include safety (pressure)relief system, hydrogen control system, environmental monitoring system,and accidental UV exposure protection system. Blower module can includetype: centrifugal; screw and the like; capacity (size): flow rates inCFM, discharge pressures, and controls. Separators and recovery modulecan include CO₂ liquefaction system for recovering CO₂ and other gasesfrom the feed, hydrogen processing system, CO₂ processing system, andsulfur processing system.

In some embodiments, the present systems can include at least twochambers coupled and in fluid communication therewith. The first chambercan be configured to receive and thermally excite an input feed thatincludes at least a portion of hydrogen sulfide. The second chamber canbe configured to receive the thermally excited feed, to decompose thehydrogen sulfide within the feed such that hydrogen and elemental sulfurresult, and to separate the hydrogen and elemental sulfur as well as anyother components that may be present in the input feed.

As discussed in more detail below, the first chamber can include amicrowave source that can be configured to expose the input feed that isflowing in and through the first chamber to microwave energy. Thisexposure can increase ability of the hydrogen sulfide to absorb energy,such as UV light, which can enhance the effectiveness of photolyticdesulfurization. Further, in some embodiments, the first chamber can beconfigured to facilitate the formation of a standing wave, which asdiscussed above, allows the hydrogen sulfide to align itself, therebyincreasing its effective cross-sectional area for UV light absorption.

Further, as discussed in more detail below, the second chamber caninclude a light source, such as a UV light source, that is configured toexpose the thermally excited feed to an effective amount ofelectromagnetic energy that can result in cleavage of thehydrogen-sulfide bonds, and thus the formation of hydrogen and elementalsulfur. While the second chamber can be coupled to a separator toisolate the elemental sulfur, in some implementations, the secondchamber can be configured to isolate the elemental sulfur from theremaining feed components present within the second chamber. The secondchamber can also be configured to separate the cleaved hydrogen from theremaining feed components.

FIG. 4B illustrates an exemplary embodiment of a desulfurization system400. As shown, the system 400 includes two chambers 402, 404 coupledtogether and in fluid communication. The first chamber 402 includes aninlet 406 that receives an input feed (not shown). The input feed can beraw or processed feed having a compositional makeup that includes atleast hydrogen sulfide. In some embodiments, the input feed can be inthe form of a vapor of a gas.

The inlet 406 can supply the input feed at a constant flow rate, whichcan vary depending on the implementation of the system. The inlet 406can include a gauge or valve to control the flow rate of the input feed.Alternatively, the flow rate of the input feed can be continuouslychanged, for example, to decrease, increase, or maintain product yield(e.g., elemental sulfur).

The first chamber 402 can also include a microwave source 408 that ispositioned proximate to the inlet 406 (e.g., at a distal end 402 d ofthe first chamber 402). The microwave source 408 emits microwave energyso as to thermally excite the hydrogen sulfide present in the input feedas it flows into and through the first chamber 402. As shown, the firstchamber 402 can be elongate and cylindrical along a primary axis (e.g.,a tube-like configuration). It is also contemplated herein that thefirst chamber 402 can have other configurations. Further, it is alsocontemplated that the first chamber 402 can be a photo-reactor similarto photo reactor 800 shown in FIG. 8 or an array of photo-reactorssimilar to array 2000 shown in FIG. 48.

The first chamber 402 can include a waveguide that is configured toguide the microwave energy through the first chamber (e.g., from thedistal end 402 d to the proximate end 402 p of the first chamber 402 inwhich the proximate end 404 p). In some embodiments, the waveguide canbe formed by a wall of the first chamber 402. In such instances, thefirst chamber 402 can be formed of a suitably reflective material suchas stainless steel. Further, at least a portion of the inner surface ofthe wall can be coated with a composition in desired areas forreflection. Alternatively, or in addition to, the first chamber 402 caninclude a separate waveguide (e.g., a waveguide that is not formed bythe wall of the first chamber).

It should be noted that in some embodiments, the first chamber caninclude an array of sub-chambers that are structured similar to firstchamber 402 as shown in FIG. 4B. The sub-chambers can be arranged inseries or in parallel.

As shown in FIG. 4B, the proximal end 402 p of the first chamber 402couples to the second chamber 404. The second chamber 404 includes alight source 410. As such, the second chamber 404 can function as aphoto-reactor. While the light source 410 can be configured to emitvarious types of light, in some implementations, the light source 410emits UV light. In one embodiment, the light source 410 radiates UVlight having a wavelength range from about 100 nm to about 300 nm, fromabout 200 nm to about 300 nm, from about 280 nm to about 300 nm, or fromabout 290 nm to about 300 nm. As shown, the light source 410 can beattached to at least a portion of the inner surface of the secondchamber 404. In one embodiment, the light source 410 can be coupled tothe entire inner surface. It is contemplated herein that the lightsource 410 can be positioned at other areas or coupled to a component ofthe second chamber 404, such as about a vortex finder 1022 in FIG. 42 asdescribed in more detail below.

The radiation time and/or the intensity of light emitted within thesecond chamber 404 can be suitably adjusted by modifying the parametersof the light source 410. The light source 410 can be suitably selectedfrom a radiating device that can intensify a particular range ofwavelengths. An exemplary light source may include LED light, laser, andthe like.

In use, as the input feed flows from the first chamber 402 and into thesecond chamber 404, the UV light emitted by the light source 410 is atleast partially absorbed by the hydrogen sulfide. As a result, bonddisassociate occurs, thereby producing hydrogen gas and elementalsulfur. While the second chamber 404 can have various shapes, the secondchamber 404, as shown in FIG. 4B, takes the form of a cyclone, andtherefore, the resulting hydrogen gas is ventilated from the secondchamber 404 through a first outlet 412 positioned at a top portionthereof. Further, the resulting elemental sulfur exits the secondchamber 404 through a second outlet 414 positioned at a bottom portionthereof. In addition, the remaining components of the feed presentwithin the second chamber 404 can ventilate with the hydrogen gasthrough the first outlet 412 or with the elemental sulfur through secondoutlet 414. Alternatively, or in addition to, the remaining componentscan ventilate from the second chamber 404 through a third outlet 416.Any outlet of the second chamber 404 can include a gauge or valve tocontrol the exit rate of the respective component(s).

Further, as shown in FIG. 4B, the second chamber 404 can include a gaspermeable membrane 418 (e.g., a proton exchange membrane) that can beconfigured to separate the hydrogen gas from the remaining components ofthe feed and/or the elemental sulfur. As shown, the gas permeablemembrane 418 substantially separates the hydrogen gas such that thehydrogen gas can ventilate through the first outlet 412 and theremaining feed component(s) can ventilate through the third outlet 416.Further, in some implementations where a reactant gas is present withinthe second chamber 404, the gas permeable membrane 418 can also beconfigured to separate the hydrogen gas from the reactant gas. In someembodiments, the gas permeable membrane 418 can include a catalyst.

As shown in FIG. 4B, the second chamber 404 can include a coolingelement 420. The cooling element 420 can be configured to control orchange the temperature of the elemental sulfur, for example, decreasethe temperature to thereby particulate the elemental sulfur. As shown,the cooling element 420 can be can be coupled to the inner surface ofthe second chamber 404. In other embodiments, the cooling element 420can be incorporated within, or coupled to the outer surface of, the wallof the second chamber 404 so as to form a jacketed second chamber. Inanother embodiment, the second chamber can be connected to a coolingdevice (e.g., heat exchanger). Non-limiting examples of suitable coolingelements include air, water, and the like of suitable temperature.

Further, the second chamber 404 can include or be connected to a heatingdevice. The heating device can be configured to control the reactiontemperature at the beginning of the decomposing reaction or during thedecomposing reaction. Non-limiting examples of suitable heating devicesinclude a flame, an electric furnace, a hot plate, and an air stream.Alternatively, or in addition to, a heating element can be incorporatedwithin, or coupled to the outer surface of, a wall of the second chamber404. Non-limiting examples of suitable heating elements include air,water, and the like of suitable temperature.

In some embodiments, the system 400 can include a controller or can bein wired or wireless communication with a controller. The controllerrefers to a hardware device that may include a memory and a processor.The memory is configured to store the modules and the processor isspecifically configured to execute said modules to perform one or moreprocesses. The control logic of the present subject matter may beembodied as non-transitory computer readable media on a computerreadable medium containing executable program instructions executed by aprocessor, controller/control unit or the like. Examples of the computerreadable mediums include, but are not limited to, ROM, RAM, compact disc(CD)-ROMs, magnetic tapes, floppy disks, flash drives, smart cards andoptical data storage devices. The computer readable recording medium canalso be distributed in network coupled computer systems so that thecomputer readable media is stored and executed in a distributed fashion,e.g., by a telematics server or a Controller Area Network (CAN). Thecontroller can be suitably connected to at least one component of thesystem, for example, the inlet, the outlets, the first chamber, thesecond chamber, the microwave source, and the light source, and controlthe reaction (decomposition condition). The controller may have acontrolling algorithm that can suitably adjust conditions of the system.

FIGS. 42-47 illustrate another exemplary embodiment of a desulfurizationsystem 1000. Aside from the differences described in detail below, thesystem 1000 can be similar to system 400 shown in FIG. 4B and istherefore not described in detail herein. Further, for purposes ofsimplicity, certain components of the system 1000 are not illustrated inFIGS. 42-47.

As shown in FIGS. 42 and 44-45, the system 1000 includes a first chamber1002 and a second chamber 1004 coupled thereto. The first chamber 1002can be a photo-reactor, like photo-reactor 800 shown in FIG. 8, or anarray of photo-reactors, like array 2000 shown in FIG. 48. In someembodiments, the first chamber 1002 is directly coupled to the secondchamber, as shown in FIGS. 42 and 44-45. In other embodiments,additional chambers or other components could be positioned between thefirst and second chambers 1002, 1004.

As shown in FIG. 42, the second chamber can include a light source 1010positioned about a vortex finder 1022 in the second chamber 1004. Whilethe light source 1010 can have a variety of configurations, as shown inFIGS. 42 and 45-47, the light source 1010 has a helical configurationthat is wrapped about the outer surface of the vortex finder 1022. Inuse, a microwave source (not shown) can radiate the microwave energyinto the second chamber 1004 such that the microwave energy contacts thelight source 1010. In some embodiments, the light source 1010 caninclude an internal gas that generates ultraviolet light upon contactwith the microwave energy.

Further, as shown in FIGS. 42 and 45-47, the second chamber 1004includes two gas permeable membranes 1018, like gas permeable membrane418 shown in FIG. 4B, and a second gas permeable membrane 1024. Thesecond gas permeable membrane is positioned at the distal end 1022 d ofthe vortex finder 1022. The second gas permeable membrane 1024 (e.g., aproton exchange membrane) can be configured similar to gas permeablemembrane 418 and therefore is not discussed in detail herein.

The present subject matter can include a refinery system that includesthe desulfurization system as described herein. The present subjectmatter can include a desulfurization system that includes the reactor asdescribed herein. In particular, the desulfurization system may includea recyclization unit for introducing the hydrogen gas produced from thereactor into another stage of a fuel processing system that utilizeshydrogen as an input.

A first experiment was conducted to confirm the presence of sulfur andsulfur was extracted from hydrogen sulfide.

FIG. 5 is a block diagram illustrating test-setup 500 and FIGS. 6 and 7illustrate photographs of the test-setup. The test-setup included ahydrogen sulfide source arranged to introduce hydrogen sulfide into aninlet of a reaction chamber including a UV-C lamp. The UV-C lamp(mercury based) is capable of irradiating gasses internal to thereaction chamber. An outlet of the UV-C lamp (reaction chamber) isconnected to a collection vessel containing water. The reaction chamberwas of approximately 115 cm in length. The UV-C lamp was driven at 234volts and 0.002 Amps.

At 1 atm and a starting temperature of the reaction chamber of 27degrees Celsius. Hydrogen sulfide was introduced into the lamp usingsodium sulfide and hydrochloric acid. The output of the UV-C lamp wasbubbled through pure water (H₂O) in the collection vessel. The hydrogensulfide was allowed to flow through the UV lamp for 15 minutes. Asillustrated in FIG. 7, left, the H₂O contained in the collection vesselturned milky, indicating sulfur was present in the output stream of thereaction chamber. After 15 minutes, the reaction chamber temperature was35 degrees Celsius.

Although a few variations have been described in detail above, othermodifications or additions are possible. For example, an ultravioletlight reactor can be used for disinfection, for cleaving bonds ofmaterial other than hydrogen sulfide (e.g., other binary and tertiarymolecules with appropriate bond disassociation energies).

One or more aspects or features of the subject matter described hereincan be realized in digital electronic circuitry, integrated circuitry,specially designed application specific integrated circuits (ASICs),field programmable gate arrays (FPGAs) computer hardware, firmware,software, and/or combinations thereof. These various aspects or featurescan include implementation in one or more computer programs that areexecutable and/or interpretable on a programmable system including atleast one programmable processor, which can be special or generalpurpose, coupled to receive data and instructions from, and to transmitdata and instructions to, a storage system, at least one input device,and at least one output device. The programmable system or computingsystem may include clients and servers. A client and server aregenerally remote from each other and typically interact through acommunication network. The relationship of client and server arises byvirtue of computer programs running on the respective computers andhaving a client-server relationship to each other.

These computer programs, which can also be referred to as programs,software, software applications, applications, components, or code,include machine instructions for a programmable processor, and can beimplemented in a high-level procedural language, an object-orientedprogramming language, a functional programming language, a logicalprogramming language, and/or in assembly/machine language. As usedherein, the term “machine-readable medium” refers to any computerprogram product, apparatus and/or device, such as for example magneticdiscs, optical disks, memory, and Programmable Logic Devices (PLDs),used to provide machine instructions and/or data to a programmableprocessor, including a machine-readable medium that receives machineinstructions as a machine-readable signal. The term “machine-readablesignal” refers to any signal used to provide machine instructions and/ordata to a programmable processor. The machine-readable medium can storesuch machine instructions non-transitorily, such as for example as woulda non-transient solid-state memory or a magnetic hard drive or anyequivalent storage medium. The machine-readable medium can alternativelyor additionally store such machine instructions in a transient manner,such as for example as would a processor cache or other random accessmemory associated with one or more physical processor cores.

To provide for interaction with a user, one or more aspects or featuresof the subject matter described herein can be implemented on a computerhaving a display device, such as for example a cathode ray tube (CRT) ora liquid crystal display (LCD) or a light emitting diode (LED) monitorfor displaying information to the user and a keyboard and a pointingdevice, such as for example a mouse or a trackball, by which the usermay provide input to the computer. Other kinds of devices can be used toprovide for interaction with a user as well. For example, feedbackprovided to the user can be any form of sensory feedback, such as forexample visual feedback, auditory feedback, or tactile feedback; andinput from the user may be received in any form, including acoustic,speech, or tactile input. Other possible input devices include touchscreens or other touch-sensitive devices such as single or multi-pointresistive or capacitive trackpads, voice recognition hardware andsoftware, optical scanners, optical pointers, digital image capturedevices and associated interpretation software, and the like.

In the descriptions above and in the claims, phrases such as “at leastone of” or “one or more of” may occur followed by a conjunctive list ofelements or features. The term “and/or” may also occur in a list of twoor more elements or features. Unless otherwise implicitly or explicitlycontradicted by the context in which it is used, such a phrase isintended to mean any of the listed elements or features individually orany of the recited elements or features in combination with any of theother recited elements or features. For example, the phrases “at leastone of A and B;” “one or more of A and B;” and “A and/or B” are eachintended to mean “A alone, B alone, or A and B together.” A similarinterpretation is also intended for lists including three or more items.For example, the phrases “at least one of A, B, and C;” “one or more ofA, B, and C;” and “A, B, and/or C” are each intended to mean “A alone, Balone, C alone, A and B together, A and C together, B and C together, orA and B and C together.” In addition, use of the term “based on,” aboveand in the claims is intended to mean, “based at least in part on,” suchthat an unrecited feature or element is also permissible.

The subject matter described herein can be embodied in systems,apparatus, methods, and/or articles depending on the desiredconfiguration. The implementations set forth in the foregoingdescription do not represent all implementations consistent with thesubject matter described herein. Instead, they are merely some examplesconsistent with aspects related to the described subject matter.Although a few variations have been described in detail above, othermodifications or additions are possible. In particular, further featuresand/or variations can be provided in addition to those set forth herein.For example, the implementations described above can be directed tovarious combinations and subcombinations of the disclosed featuresand/or combinations and subcombinations of several further featuresdisclosed above. In addition, the logic flows depicted in theaccompanying figures and/or described herein do not necessarily requirethe particular order shown, or sequential order, to achieve desirableresults. Other implementations may be within the scope of the followingclaims.

What is claimed is:
 1. A method comprising: providing hydrogen sulfideinto a first chamber adjacent a second chamber; contacting the hydrogensulfide with microwave energy within the first chamber, the microwaveenergy generated by a microwave source; providing the hydrogen sulfideto the second chamber, the second chamber including an outlet and awaveguide, wherein an ultraviolet light source resides within thewaveguide of the second chamber; contacting the hydrogen sulfide withultraviolet light within the second chamber, the ultraviolet lightgenerated by the ultraviolet light source, wherein contacting of thehydrogen sulfide with the ultraviolet light results in hydrogen gas andsulfur; and separating at least a portion of the hydrogen gas from thesulfur using a gas permeable membrane to allow the separated hydrogengas to ventilate through the outlet of the second chamber, wherein thegas permeable membrane resides within the second chamber.
 2. The methodof claim 1, wherein the microwave source is further configured toradiate the microwave energy into the waveguide of the second chambersuch that the microwave energy contacts the ultraviolet light source,the ultraviolet light source including an internal gas that generatesthe ultraviolet light upon contact with the microwave energy.
 3. Themethod of claim 1, wherein the waveguide includes an end configured suchthat the microwave energy forms a standing wave within the waveguide. 4.The method of claim 1, wherein the second chamber further includes: afirst electrode configured to have a negative charge; and a secondelectrode configured to have a positive charge, the first electrode andthe second electrode being external to the ultraviolet light source andinternal to the waveguide.
 5. The method of claim 1, wherein thehydrogen sulfide is provided to a plurality of tube assemblies adjacentthe first chamber, each of the plurality of tube assemblies including atube assembly outlet, a plurality of ultraviolet light sources eachresiding within a respective one of the plurality of tube assemblies,wherein the microwave source is configured to radiate the microwaveenergy into the first chamber and into the plurality of tube assembliessuch that the microwave energy contacts the plurality of ultravioletlight sources, the plurality of ultraviolet light sources including theinternal gas that generates ultraviolet light upon contact with themicrowave energy.
 6. The method of claim 1, further comprising:separating, using a gas-solid separator, the sulfur from the hydrogengas.
 7. The method of claim 1, wherein the ultraviolet light sourceradiates the ultraviolet light having a wavelength that ranges fromabout 280 nm to 300 nm.
 8. The method of claim 1, wherein the secondchamber is elongate and extends along a primary axis, the ultravioletlight source is elongate along the primary axis and resides within thesecond chamber along the primary axis, wherein the second chamberfurther includes: a first electrode configured to have a negativecharge; and a second electrode configured to have a positive charge, thefirst electrode and the second electrode being external to theultraviolet light source and internal to the waveguide; wherein thefirst electrode is elongate along the primary axis and is arranged abovethe ultraviolet light source and the second electrode is elongate alongthe primary axis and is arranged below the ultraviolet light source. 9.The method of claim 1, wherein a temperature for decomposing thehydrogen sulfide is performed at a temperature range of about 0 to 125degrees Celsius.
 10. The method of claim 1, wherein the hydrogen sulfideis provided into the first chamber at a pressure of about 0.1 to 10 atm.11. The method of claim 1, wherein the ultraviolet light and themicrowave energy is contacted with the hydrogen sulfide for about 0.01seconds to 15 minutes.
 12. The method of claim 1, further comprisingcollecting the hydrogen sulfide from natural gas or processing petroleumoil to generate the hydrogen sulfide.
 13. The method of claim 1, whereinthe second chamber forms a hydrocyclone.
 14. The method of claim 13,wherein the ultraviolet light source resides on a vortex finder locatedwithin the hydrocyclone.